WO2014189077A1 - Multi-point probe and electronic contact sheet for configuring same, multi-point probe array and multi-point probe manufacturing method - Google Patents

Abstract

The multi-point probe is obtained from a tubular laminate configured by winding an electronic contact sheet, which has multiple electronic contacts disposed on a sheet-shaped insulating base material so as to be separated from each other and multiple wires connected to the respective electronic contacts, from one edge to the other edge to laminate same in multiple layers. The sheet is laminated so that the electronic contacts are not covered by the sheet-shaped insulating base material but exposed and, except for the wires of the outermost layer, at least a portion of the wires is covered by the sheet-shaped insulating base material.

Description

Multi-point probe, electronic contact sheet constituting the same, multi-point probe array, and method for manufacturing multi-point probe

The present invention relates to a multipoint probe, an electronic contact sheet constituting the multipoint probe, a multipoint probe array, and a method for manufacturing the multipoint probe.
This application claims priority based on Japanese Patent Application No. 2013-107229 for which it applied to Japan on May 21, 2013, and uses the content here.

Detecting biological signals emitted from the surface and inside of a living body not only grasps the current state of health, but also makes it possible to detect possible future diseases in advance, thereby creating a healthy and rich society. It is attracting attention as a next-generation medical technology to be realized.

It is extremely important to detect this biological signal with high spatial resolution in order to investigate the disease in detail.
For example, the detection of an electrical signal of a biological tissue such as the brain or spinal cord is performed by inserting a probe having a plurality of voltage detection electronic contacts formed at the tip thereof into the brain (for example, Patent Documents 1 and 2).

The probe disclosed in Patent Document 1 is configured to include an electronic contact and wiring connected thereto on a sheet-like or plate-like insulating base (hereinafter referred to as “flat insulating base” as appropriate).
In addition, the probe disclosed in Patent Document 2 is configured to include a probe electronic contact that is erected on a flat insulating substrate and wiring that is connected to the probe electronic contact.
On the other hand, a sheet-like insulating base material formed with an electronic contact such as an electronic contact or a sensor for detecting an electrical signal on the side surface of a tubular structure, for example, a catheter or an endoscope, is spirally wound to be electrically and chemically A device for detecting mechanical and mechanical biological signals has been proposed by the present inventors (Non-Patent Document 1). In this method, it is possible to arrange a large number of electrical contacts on the surface of the tubular structure.
In addition, in a device applied to a living body, not only the detection of a living body signal but also a configuration in which living body information is detected by a combination of an electronic contact that gives a stimulus to the living body and an input / output electronic contact that detects a stimulus applied to the living body and its response It has been known.

Japanese Patent No. 4,406,697 JP 2012-130519 A

However, although the electrical signals of one part of the brain can be examined by the probes disclosed in Patent Documents 1 and 2, the three-dimensional spatial resolution is not sufficient, and signal transmission between many parts of the brain is not possible. In order to investigate, there is a demand for a probe in which electronic contacts are formed in a wide range at an extremely high density.
Further, in the sheet-like probe disclosed in Non-Patent Document 1, when electronic contacts are formed in a wide range and at a high density, the spiral winding distance becomes longer, the number of wires is remarkably increased, and the wiring resistance is increased. There are problems such as a decrease in signal detection accuracy due to, and the number of electronic contacts being limited by the number of wires.

The present invention has been made in view of the above circumstances, and a multipoint probe capable of realizing a remarkably high spatial resolution as compared with conventional probes, and an electronic contact sheet, a multipoint probe array, and a multipoint probe constituting the multipoint probe. An object is to provide a manufacturing method.

In order to solve the above problems, the present invention employs the following means.
A multipoint probe according to an aspect of the present invention is an electron having a plurality of electronic contacts arranged in a row in a sheet-like insulating base and a plurality of wirings connected to each electronic contact. A contact point sheet is a multipoint probe comprising a tubular laminate formed by laminating a contact sheet from one end to the other end, and the electronic contact is the sheet-like insulating substrate. It is exposed without being covered, and the wiring is laminated so that at least a part of the wiring other than the wiring of the uppermost layer is covered with the sheet-like insulating substrate.
In the present specification, the “electronic contact” means a part through which a current flows widely, such as an electrode.

A multipoint probe according to an aspect of the present invention is characterized in that, in the multipoint probe described above, an axial core material is provided, and the electronic contact sheet is wound around an outer peripheral surface of the core material.

The multipoint probe which concerns on 1 aspect of this invention is the said multipoint probe, The said several electronic contact is along the edge part of the one end side of the said electronic contact sheet in one surface of the said sheet-like insulating base material. It is characterized by being arranged.

In the multipoint probe according to an aspect of the present invention, in the multipoint probe, the sheet-like insulating base material is formed such that the edge portion recedes from one end to the other end of the tubular laminate. It is characterized by.

The multi-point probe according to an aspect of the present invention is characterized in that, in the multi-point probe, the plurality of electronic contacts are arranged in a spiral shape with respect to an axis of the tubular laminate.

In the multipoint probe according to one aspect of the present invention, in the multipoint probe, the plurality of wirings extend along a direction of an axis of the tubular laminate over a predetermined range starting from the plurality of electronic contacts. It is characterized by being.

In the multipoint probe according to one aspect of the present invention, in the multipoint probe, a plurality of pads connected to each wiring and connected to an external circuit extend along the other end in the vicinity of the other end of the electronic contact sheet. It is characterized by being arranged.

In the multipoint probe according to an aspect of the present invention, in the multipoint probe, the electronic contact sheet is covered with a first insulating material so that a plurality of electronic contacts and a plurality of pads are exposed. Features.

In the multipoint probe according to one aspect of the present invention, in the multipoint probe, a first shield conductive film is formed on the other surface of the sheet-like insulating base on which the wiring is disposed. It is characterized by.

In the multipoint probe according to an aspect of the present invention, in the multipoint probe, a second shield conductive film is formed on a surface of the sheet-like insulating base material on which the wiring is disposed. Features.

The multi-point probe according to an aspect of the present invention is characterized in that, in the multi-point probe, the sheet-like insulating base has an amplifier connected to the plurality of electronic contacts.

The multi-point probe array according to an aspect of the present invention is characterized in that a plurality of the multi-point probes are provided separately on the base substrate.

The electronic contact sheet according to an aspect of the present invention is an electronic contact sheet that constitutes the multipoint probe.

The manufacturing method of the multipoint probe which concerns on 1 aspect of this invention is a manufacturing method of the said multipoint probe, Comprising: The said electronic contact sheet | seat is directed toward the other end so that the said several electronic contact may be exposed. The second insulating material is entirely covered with the second insulating material, and then the second insulating material on the plurality of electronic contacts and the plurality of pads is removed.

According to the multipoint probe according to one aspect of the present invention, the electronic contact sheet is composed of a tubular laminate formed by laminating multiple layers by winding the electronic contact sheet from one end to the other end. By adopting a structure that is exposed without being covered with a sheet-like insulating substrate, the electronic contacts can be integrated and placed on the surface of the multipoint probe, enabling high-density electronic contact placement and high spatial resolution. Thus, it is possible to detect an electric signal, apply an electrical stimulus, and the like. By adopting a configuration in which the electronic contact sheet is wound so that at least a part of the wiring other than the uppermost layer wiring is laminated so as to cover the sheet-like insulating base material, a multilayer wiring structure is obtained. Higher density wiring is possible compared to probes that are not wound with an insulating base material on which electronic contacts are arranged (hereinafter referred to as “non-winding probes” as appropriate). As a result, high-density electronic contact arrangement is possible. It becomes. By increasing the number of windings, it is possible to arrange electronic contacts at a much higher density than conventional non-winding probes, and to detect a large number of simultaneous signals. In addition, the multipoint probe of the present invention requires a simple wiring layout and a low wiring density compared to a high-density electronic contact arrangement comparable to that of a conventional non-winding probe.

According to the multipoint probe which concerns on 1 aspect of this invention, it was equipped with the axial core material, and the electronic contact sheet employ | adopted the structure wound by the outer peripheral surface of the core material, Therefore An electronic contact is made into axial shape. Since they can be arranged and arranged on the outer peripheral surface of the core material, high-density electronic contact arrangement is possible, and electrical signals can be detected and electrical stimulation can be applied with high spatial resolution. A more flexible multipoint probe can be realized by winding the electronic contact sheet around the core material and then removing the core material. Moreover, when it uses in the living body with the structure which extracted the core material, it can reduce that a biological body is damaged by vibration.

According to the multipoint probe according to one aspect of the present invention, the plurality of electronic contacts employs a configuration in which the electronic contact sheet is disposed along one edge of the electronic contact sheet on one surface of the sheet-like insulating base material. Therefore, it is possible to arrange electronic contacts at high density on the outer peripheral surface of the tubular laminate. For example, in the case of a rectangular electronic contact sheet, it is possible to arrange the contact points densely with respect to the axis of the tubular laminate by simply winding the edge so that the edge is inclined with respect to the axis, and the electronic contacts can be arranged with high density. .

According to the multipoint probe according to one aspect of the present invention, the sheet-like insulating base material employs a configuration in which the edge portion is formed so as to recede from one end of the tubular laminate to the other end. The electronic contact is arranged along the edge, and the electronic contact sheet is wound around the core so that the edge is inclined with respect to the axis of the tubular laminate, and the axis of the tubular laminate is The electronic contacts can be arranged at high density.

According to the multipoint probe according to one aspect of the present invention, since the plurality of electronic contacts employs a configuration in which the plurality of electronic contacts are arranged in a spiral manner with respect to the axis of the tubular laminate, electrons are disposed on the outer peripheral surface of the tubular laminate. Electronic contacts can be arranged with high density by arranging contacts closely.

According to the multipoint probe according to an aspect of the present invention, the plurality of wirings are configured by adopting a configuration that extends along the axial direction of the tubular laminated body over a predetermined range starting from the plurality of electronic contacts. Compared with the structure which inclines with respect to the axial direction of a tubular laminated body, the frequency | count of superimposition of wiring decreases and crosstalk can be reduced. In addition, since the portion where the wiring is formed becomes thicker than the portion where the wiring is not formed, the multilayer wiring structure is thinned by reducing the number of overlapping times. In addition, since the wiring layout is simple, high-density wiring is possible.

According to the multipoint probe according to one aspect of the present invention, a plurality of pads are arranged along the other end in the vicinity of the other end of the electronic contact sheet, thereby arranging a large number of pads. As a result, high-density electronic contact arrangement is possible. That is, the other end of the electronic contact sheet is a portion remaining on the outermost surface of the probe after winding, and is not covered with the electronic contact sheet, so that it can be arranged with high density. On the other hand, for example, when the end portion located between the one end and the other end of the electronic contact sheet covers the electronic contact sheet by winding, a pad is formed at this end portion. The pad can be formed only in the range of the outer periphery of the tubular laminate on the other end side. Therefore, a large number of pads cannot be formed, and as a result, the electronic contacts cannot be arranged with high density.

According to the multipoint probe according to an aspect of the present invention, the electronic contact sheet employs a configuration in which the plurality of electronic contacts and the plurality of pads are covered with the first insulating material so that wiring is provided. Covering with the first insulating material ensures the insulation. By winding the electronic contact sheet, the surface of the wiring is covered by the other surface of the sheet-like insulating base material, so that insulation is secured. It will be certain.

According to the multipoint probe according to one aspect of the present invention, by adopting the configuration in which the first shield conductive film is formed on the other surface of the surface on which the wiring is disposed, Crosstalk between wirings is reduced.

According to the multipoint probe according to one aspect of the present invention, by adopting the configuration in which the second shield conductive film is formed on the surface on which the wiring is disposed, the wiring between the layers in the multilayer wiring structure is provided. Crosstalk is reduced.

According to the multipoint probe of one aspect of the present invention, a weak signal (input voltage) is effectively obtained by adopting a configuration having an amplifier connected to a plurality of electronic contacts on a sheet-like insulating substrate. Can be amplified.

According to the manufacturing method of the multipoint probe which concerns on 1 aspect of this invention, after winding an electronic contact sheet | seat toward the other end from the one end so that said several electronic contact may be exposed, it is 2nd on the whole. Since the structure in which the second insulating material on the plurality of electronic contacts and the plurality of pads is removed thereafter is employed, a multi-point probe that is reliably insulated can be manufactured.

It is a perspective view which shows an example of the multipoint probe which concerns on one Embodiment of this invention. It is a schematic diagram which shows the state which wound up the electronic contact sheet | seat wound up for description about the multipoint probe shown in FIG. It is a model for demonstrating other electronic contact arrangement | positioning of the multipoint probe of this invention. It is a perspective view which shows an example of the multipoint probe which concerns on other embodiment of this invention. 1 shows a composition or a conductive material that can be used for an electronic contact material of a multipoint probe of the present invention, wherein (a) shows a case where carbon nanotubes covered with molecules constituting DEMEBF ₄ are dispersed in a polyrotaxane. (B) is a photograph of a sheet obtained by photocrosslinking the composition shown in (a), and (c) is a photocrosslink of the composition shown in (a). And an optical micrograph of a patterned fine structure having a line width of about 50 μm. It is a high-resolution cross-sectional transmission electron microscope image (TEM image), (a) is a TEM image of carbon nanotubes that can be used for the electronic contact material of the multipoint probe of the present invention, (b) without ionic liquid, It is a TEM image of carbon nanotubes covered with polyrotaxane obtained by mixing carbon nanotubes and polyrotaxane in water and stirring while subdividing with a jet mill, and (c) is shown in FIG. 1 (a). It is a TEM image of the carbon nanomaterial or composition obtained on the same conditions as the preparation conditions of a composition. It is a graph which shows the surface resistance of the composition (or electroconductive material) which can be used for the electronic contact material of the multipoint probe of this invention, and its carbon nanotube content dependency. It is a graph which shows the electrical capacitance of the composition (or electroconductive material) which can be used for the electronic contact material of the multipoint probe of this invention, and its frequency dependence. It is a flowchart for demonstrating the manufacturing method of the electroconductive material which can be used for the electronic contact material of the multipoint probe of this invention. It is a flowchart which shows the application example of the manufacturing method of the electroconductive material which can be used for the electronic contact material of the multipoint probe of this invention. It is the photograph which shows the result of having investigated the dispersibility of a carbon nanotube, (A) is a photograph which shows the state after putting a carbon nanotube in deionized water and stirring for one week, (B) is a carbon nanotube and DEMEBF. ₄ is a photograph showing a state after ₄ is put into deionized water and stirred for one week in the same manner. (C) is a photo of carbon nanotubes put into deionized water and stirred for one week in the same manner, and then a jet mill. (D) shows a state after carbon nanotubes and DEMEBF ₄ 60 mg were put into deionized water, similarly stirred for 1 week, and then treated with a jet mill. It is a photograph, (E) Carbon nanotubes, DEMEBF ₄ and microfibrillated cellulose are put into deionized water and stirred for one week in the same manner. It is a photograph which shows the state after processing the obtained paste with a jet mill after that. It is a perspective view which shows an example of the multipoint probe array which concerns on one Embodiment of this invention. It is a flowchart of the manufacturing process of the multipoint probe array which concerns on one Embodiment of this invention. It is a perspective view which shows an example of the multipoint probe which concerns on other embodiment of this invention.

Hereinafter, a configuration of a multipoint probe to which the present invention is applied, an electronic contact sheet constituting the multipoint probe, a multipoint probe array, and a multipoint probe manufacturing method will be described with reference to the drawings. In addition, in the drawings used in the following description, in order to make the features easy to understand, there are cases where the portions that become the features are enlarged for convenience, and the dimensional ratios of the respective components are not always the same as the actual ones. . In addition, the materials, dimensions, and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be appropriately changed and implemented without changing the gist thereof. In addition, the multipoint probe, the electronic contact sheet, and the multipoint probe array of the present invention may include components such as layers that are not described below as long as the effects of the present invention are not impaired.

(Multi-point probe)
FIG. 1 is a perspective view showing an example of a multipoint probe according to an embodiment of the present invention. FIG. 2 is a schematic view showing a state in which the electronic contact sheet that has been wound for the purpose of explanation is unwound from the multipoint probe shown in FIG. 1 and 2 show a multi-point probe having a configuration including a core material.
In addition, in description of a multipoint probe, the electronic contact sheet which concerns on one Embodiment of this invention is also demonstrated.

The multipoint probe 100 includes a plurality of electronic contacts 2 that are spaced apart from each other on the sheet-like insulating substrate 1, a plurality of wirings 3 (3a, 3b, 3c) connected to the respective electronic contacts 2, An electronic contact sheet 10 having a plurality of pads 4 connected to the wiring 3 and connected to an external circuit (not shown) is laminated in multiple layers by winding from one end 10a to the other end 10b. In the multi-point probe made of the tubular laminated body 10A, the electronic contact 2 is exposed without being covered with the sheet-like insulating substrate 1, and the wiring 3 is other than the uppermost wiring 3a (that is, FIG. 1). Are interconnected so that at least a part thereof is covered with a sheet-like insulating base material. The multipoint probe shown in FIG. 1 has a configuration including a plurality of pads, but these pads are not essential components for the multipoint probe of the present invention.

The multipoint probe 100 shown in FIGS. 1 and 2 further includes a shaft-shaped core member 20, and the electronic contact 2 is wound around the outer peripheral surface 20 a of the core member 20. The structure which is not provided with may be sufficient. The shaft-shaped core material may be used as a configuration in which the multi-point probe is detachably attached to the core material at an appropriate timing, for example, after mounting. By adopting a configuration in which the multipoint probe does not have a core material, a more flexible multipoint probe can be realized. Moreover, when using it in the living body with the structure which extracted the core material, it can reduce that a biological body is damaged by vibration.
Moreover, in the multipoint probe shown in FIG. 1, the rod-shaped core member is shown as a shaft-like core material. However, as long as the sheet-like insulating base material can be wound, the rod-like probe is not limited to a rod shape and is flexible. It may be a thing, and the thing whose hardness changes with conditions, such as temperature, may be used.
FIGS. 14A and 14B show a part of an example of a multi-point probe using a flexible shaft-like core material. Examples of applications of such multipoint probes include catheters and endoscopes.

The electronic contact sheet 10 has a plurality of electronic contacts 2, a plurality of wirings 3, and a plurality of pads 4 on one surface 1 a of the sheet-like insulating substrate 1.

The multipoint probe 100 has a wiring structure in which an electronic contact sheet 10 provided with wiring 3 is wound on one surface 1a of the insulating base material 1, and thus a layer (sheet) on which wiring is formed is laminated. is doing. Although it is very time-consuming to produce such a multilayer wiring structure by a conventional method, in the multipoint probe of the present invention, a multilayer wiring structure is formed only by winding. As the number of turns of the layer (sheet) on which the wiring is formed is increased, the total number of wirings can be increased, and as a result, the number of electronic contacts that can be arranged can be increased. Thus, by arranging a large number of electronic contacts on the surface, it is possible to arrange electronic contacts with high density, thereby enabling detection of electrical signals, application of electrical stimulation, etc. with high spatial resolution.

The sheet-like insulating substrate 1 is made of a flexible insulating material that can be wound. Specifically, for example, polyimide, polyethylene terephthalate, polyethylene naphthalate, polyetheretherketone, paraxylylene, and the like are used. Examples include polymer materials. Further, by using an elastomer such as silicon rubber for the insulating substrate 1, a flexible multipoint probe can be realized in combination with a flexible core material.
The thickness is not limited, but for example, a thickness of 1 μm to 20 μm can be used. For example, if a sheet-like insulating substrate having a thickness of 1 μm is used, the thickness of the laminated multilayer sheet is about 30 μm even if the sheet is wound 30 times.

The shape of the sheet-like insulating substrate 1 is not particularly limited, but the sheet-like insulating substrate (that is, the electronic contact sheet) needs to be wound so that the plurality of electronic contacts 2 are exposed.
For example, when a plurality of electronic contacts are arranged along a side edge between one end and the other end of a rectangular sheet-like insulating base material, the plurality of electronic contacts are exposed. Then, it is wound so as to be inclined with respect to the axis of the tubular laminated body 10A (in the case of the configuration shown, coincides with the axis of the core 20).

In the example shown in FIG.1 and FIG.2, the sheet-like insulating base material 1 has the 1st rectangular part 1b in the predetermined range from the end (start end) from which winding is started to the core material 20, First, the edge 1c on the one end 20b side of the core member 20 is formed so as to recede from the one end 20b of the core member 20 toward the other end 20c, and the pad 4 is attached to the end (other end) 1d opposite to the start end. Is a shape having a second rectangular portion (near the other end) 1e. The opposite edge 1f of the edge 1c is formed without retreating from the edge of the first rectangular part 1b.
In the example shown in FIGS. 1 and 2, the plurality of electronic contacts 2 are arranged along the edge portion 1c, and the plurality of pads 4 are the other in the second rectangular portion (near the other end) 1e. Arranged along the end 1d.
1 and 2, the sheet-like insulating base material 1 is formed so that the edge portion 1c on the one end 20b side of the core material 20 is retracted from the one end 20b of the core material 20 toward the other end 20c. By making the electronic contact sheet 10 having a configuration in which a plurality of electronic contacts 2 are arranged along the edge portion 1c, the sheet is only wound without being inclined with respect to the axis of the core member 20. Thus, the plurality of electronic contacts 2 are exposed.

The electronic contact 2 serves as an interface for detecting an electrical signal by touching the object and applying an electrical stimulus according to the application of the multipoint probe.
The electronic contacts 2 are arranged apart from each other on the surface 1a opposite to the surface wound around the core member 20 of the sheet-like insulating substrate 1, and the number of the electronic contacts 2 is not particularly limited, and the area of the outer peripheral surface is large. Many electronic contacts can be arranged by using a large core material.
The electronic contacts 2 are preferably arranged at intervals of 10 to 200 μm, and the diameter of each electronic contact 2 is preferably 5 to 100 μm. The shape is not particularly limited, and may be, for example, a round shape or a square shape.

The arrangement of the electronic contacts 2 is not particularly limited. For example, the electronic contacts 2 may be arranged along the edge portion 1c on one end side of the electronic contact sheet 10, and as shown in FIG. It is good also as a structure arrange | positioned spirally on the basis (in the case of the structure shown in figure, it corresponds with the axis line of the core material 20), and as shown in FIG. The structure to arrange | position and the structure arrange | positioned in 3 or more rows may be sufficient.

Further, as the material of the electronic contact 2, it is preferable to use a metal material that is not easily corroded, such as gold or platinum.
Moreover, you may use flexible nanomaterials, such as a carbon nanotube (CNT), as a material of the electronic contact 2. FIG.
For example, a gel-like structure in which a carbon nanomaterial that is doubly coated with a molecule constituting a hydrophilic ionic liquid and a water-soluble polymer is dispersed in a water-soluble polymer medium and the water-soluble polymer is crosslinked. Alternatively, a conductive material (conductive gel) may be used. This conductive gel will be described later.

The wiring 3 connects the corresponding electronic contact 2 and the pad 4. Similarly to the electronic contact 2, the surface of the sheet-like insulating base 1 opposite to the surface wound around the core member 20. They are arranged apart from each other in 1a.
The wiring 3 is preferably arranged at intervals of 5 to 200 μm, and the width is preferably 2 to 100 μm.
Further, as the material of the wiring 3, it is preferable to use a metal material that is not easily corroded, such as gold or platinum.

The wiring 3 can arrange many wiring by using the sheet-like insulating base material 1 having a wide width (length in the winding direction). Even if the number of wires is increased by using a very wide sheet-like insulating base material 1, these wires can be accumulated on the outer peripheral surface of the core material, so that the entire multipoint probe can be integrated. The size does not need to be increased.

In the example shown in FIGS. 1 and 2, the wiring 3 extends along the axial direction of the core member 20 over a predetermined range starting from the electronic contact 2. That is, the wiring 3 extends from the electronic contact 2 to the edge 1 f side along the axial direction of the core member 20. From there, it extends to the pad 4 arranged at the second rectangular portion 1d at a different angle.
The configuration in which the wiring 3 extends along the axial direction of the core material 20 is shorter in the length of the wiring and the number of superpositions than the configuration in which the wiring is inclined with respect to the axial direction of the core material, and crosstalk is reduced. Can be reduced.

The pad 4 is connected to the corresponding wiring 3 and is connected to an external circuit such as an electric signal measuring instrument or a voltage applying device according to the use of the multipoint probe, and is similar to the electronic contact 2 and the wiring 3. In addition, the sheet-like insulating base material 1 is disposed so as to be separated from each other on the surface 1 a opposite to the surface wound around the core material 20.
The pads 4 are preferably arranged at intervals of 50 to 1000 μm, and the width of the pads 4 is preferably 20 to 500 μm. The shape is not particularly limited, and examples thereof include a round shape and a square shape. Moreover, the structure which makes mounting easy by taking a staggered arrangement of pads in a plurality of stages can be taken.

As shown in FIG. 2, the pad 4 may be arranged along the other end 10b in the vicinity of the other end 10b of the electronic contact sheet 10 (position of the second rectangular portion 1e). In this configuration, since the other end 10b of the electronic contact sheet 10 is a portion remaining on the outermost surface of the probe after winding, it is not covered with the electronic contact sheet, so that the electronic contact sheet 10 can be arranged with high density. A large number of electronic contacts can be arranged. On the other hand, for example, in the configuration in which the pads are arranged along the edge 1f of the sheet-like insulating base material 1 located between the one end 10a and the other end 10b of the electronic contact sheet 10, the edge 1f Since the electronic contact sheet covers and overlaps by winding, the pad can be arranged only about the length of the outer periphery of the rod of the core material 10. Therefore, a large number of pads cannot be formed, and as a result, the electronic contacts cannot be arranged with high density.

Further, as the material of the pad 4, a metal material that is not easily corroded, such as gold or platinum, can be used.
As the material of the pad 4, similarly to the electronic contact 2, a flexible nanomaterial such as a carbon nanotube (CNT) may be used, or the gel-like conductive material (conductive gel) may be used.

The core material 20 has a shaft shape, and there is no limitation on its shape as long as the electronic contact sheet can be wound and fixed, but it is preferably a columnar shape from the viewpoint of ease of winding and fixing. .
Moreover, the tip part to be inserted into a target to detect an electrical signal or to apply an electrical stimulus may have a tapered shape from the viewpoint of ease of insertion as shown in FIGS. 1 and 2. preferable.

There is no restriction | limiting in particular in the diameter and length of the core material 20, and it can select according to a use.
The material of the core material 20 is not limited, but for example, a flexible metal such as stainless steel, tungsten, titanium, etc., engineering plastics such as polyacetal, silicon rubber, polypropylene, polyethylene, polyethylene terephthalate, etc. The resin which has can be used.

The electronic contact sheet 10 has a configuration in which a first insulating material (not shown) is coated on one surface 1a of the sheet-like insulating base 1 so that the plurality of electronic contacts 2 and the plurality of pads 4 are exposed. Also good.
Although it does not limit as a material of the 1st insulating material, Parylene (registered trademark) and Cytop (registered trademark) can be used, for example. Parylene can be coated by, for example, CVD, and cytop by dipping.
The thickness of the coating layer of the first insulating material is preferably 1 to 10 μm.

The electronic contact sheet 10 may have a configuration in which a first shield conductive film (not shown) is formed on the back surface of the one surface 1 a of the sheet-like insulating base material 1. In this configuration, crosstalk between wirings in the multilayer wiring structure is reduced.
Although it does not limit as a material of a 1st shield conductive film, Gold can be mentioned, for example.
The thickness of the first shield conductive film is preferably 0.02 to 0.2 μm.

As shown in FIG. 4, the electronic contact sheet 10 may have a configuration in which a second shield conductive film 6 is formed on the one surface 1 a of the sheet-like insulating substrate 1. In this configuration, crosstalk between wirings in the multilayer wiring structure is reduced.
Although the material of the second shield conductive film is not limited, for example, gold can be used. The thickness of the second shield conductive film is preferably 0.02 to 0.2 μm. . This second conductive film can be formed simultaneously with the wiring.

It is good also as a structure provided with both the 1st shield conductive film and the 2nd shield conductive film.

The electronic contact sheet 10 may have an amplifier connected to a plurality of electronic contacts 2 on one surface 1a of the sheet-like insulating substrate 1.

When the electronic contact sheet 10 is wound around the outer peripheral surface 20a of the core member 20, one end 10a of the electronic contact sheet 10 is fixed to the outer peripheral surface 20a of the core member 20 using an epoxy adhesive or an acrylate adhesive. After that, for example, every time one turn is wound, the front surface and the back surface of the electronic contact sheet 10 are bonded using an adhesive, and the winding is continued. The back surface of the end 10b is adhered to the front surface of the electronic contact sheet 10 using an adhesive to complete the winding.

In the multipoint probe of the present invention, the electronic contact sheet 10 is wound around the outer peripheral surface 20a of the core member 20, and then the second insulating material is entirely covered, and then the second contact points on the plurality of electronic contacts and the plurality of pads. The structure which removed these insulating materials and exposed them may be sufficient.
Although it does not limit as a material of a 2nd insulating material, Parylene (registered trademark) and Cytop (registered trademark) can be used, for example.
Since the step of the wound electronic contact sheet is covered by the configuration in which the whole is covered with the second insulating material, the multipoint probe can be easily inserted into the target.
As a method of removing the second insulating material on the plurality of electronic contacts and the plurality of pads, for example, there is a method using a laser.

The multipoint probe of the present invention can be used to detect electrical signals of biological tissues such as the brain and spinal cord and to apply electrical stimulation to biological tissues, but also to exchange signals with nerve cells and muscle cells, calcium ions It can also be used for applications such as glucose concentration measurement. Further, the application target is not limited to a living body. For example, it can be used for sensors such as ultrasonic sensors and optical sensors, and elements such as light emitting elements and ultrasonic elements. By incorporating these sensors into the surface of a catheter or endoscope, it is possible to expand the application range of examinations and treatments.

(Gel-like conductive material (conductive gel))
As described above, as a material for the multi-point probe, the electronic contact, and the multi-point probe array of the present invention, carbon double-coated with a molecule constituting a hydrophilic ionic liquid and a water-soluble polymer A gel-like conductive material (conductive gel) in which a nanomaterial is dispersed in a water-soluble polymer medium and the water-soluble polymer is crosslinked can be used.

In this specification, the ionic liquid is also referred to as a normal temperature molten salt or simply a molten salt, and is a salt that exhibits a molten state in a wide temperature range including normal temperature.
As the hydrophilic ionic liquid, a hydrophilic ionic liquid among various conventionally known ionic liquids can be used. For example, N, N-diethyl-N-methyl-N- (2-methoxy Mention may be made of ethyl) ammonium tetrafluoroborate (DEMEBF ₄ ).

In this specification, the carbon nanomaterial is a component composed of carbon atoms and structured in a nanometer size (for example, one CNT), and the carbon atoms of the component are generally van der Waals forces. For example, carbon nanotubes, carbon nanofibers (of carbon fibers having a diameter of 10 nm or less), carbon nanohorns, and fullerenes. A fine carbon nanomaterial of 10 nm or less exhibits good dispersibility in water.

Only the same kind of carbon nanomaterials may be used, or a plurality of kinds may be used.

The carbon nanotube has a structure in which a graphene sheet in which carbon atoms are arranged in a hexagonal network is a single layer or a multilayer and is rounded in a cylindrical shape (single-wall nanotube (SWNT), double-wall nanotube (DWNT), multilayer The carbon nanotube that can be used as the carbon nanomaterial is not particularly limited, and any of SWNT, DWNT, and MWNT may be used. Carbon nanotubes can generally be produced by laser ablation, arc discharge, thermal CVD, plasma CVD, gas phase, combustion, etc., but carbon nanotubes produced by any method may be used. A plurality of types of carbon nanotubes may be used.

Carbon nanotubes are likely to aggregate due to van der Waals forces between the carbon nanotubes, and usually a plurality of carbon nanotubes exist as bundles or aggregates. However, in the presence of an ionic liquid, the bundle or aggregate can be subdivided by applying a shearing force (reducing entanglement of carbon nanotubes). By sufficiently subdividing, the van der Waals force that binds the carbon nanotubes is weakened and separated into individual carbon nanotubes, and the ionic liquid can be adsorbed to the individual carbon nanotubes. As a result, a composition comprising a carbon nanotube and an ionic liquid, including a single carbon nanotube covered with molecules of the ionic liquid, can be obtained.
The means for applying the shearing force used in the subdividing step is not particularly limited, and a wet pulverizing apparatus capable of applying the shearing force, such as a ball mill, a roller mill, or a vibration mill, can be used.

By mixing the carbon nanotubes with the ionic liquid and performing the above fragmentation step, the ionic liquid molecules bonded to the surface of the carbon nanotubes with reduced entanglement by the “cation-π” interaction are connected via the ionic bonds. (Patent Document 2), as described later, the gel composition is rinsed with, for example, physiological saline, ethanol, etc. A single ionic liquid molecule layer can be formed on the surface, and by mixing water and a water-soluble polymer, the carbon nanotubes covered with the molecules constituting the ionic liquid are converted into a water-soluble polymer medium. A composition dispersed therein can be prepared.

In the present specification, the water-soluble polymer (medium) is not particularly limited as long as it is a polymer that can be dissolved or dispersed in water, and more preferably a polymer that can be crosslinked in water. For example, the following examples can be given.
1. Synthetic polymer (1) ionic polyacrylic acid (anionic)
Polystyrene sulfonic acid (anionic)
Polyethyleneimine (cationic)
MPC polymer (Zwitterion)
(2) Nonionic polyvinyl pyrrolidone (PVP)
Polyvinyl alcohol (polyvinyl acetate saponified product)
Polyacrylamide (PAM)
Polyethylene oxide (PEO)
2. Natural polymers (mostly polysaccharides)
Starch Gelatin Hyaluronic acid Alginic acid Dextran protein (eg water-soluble collagen)
3. Semi-synthetic polymer (eg cellulose solubilized)
Carboxymethylcellulose (CMC)
Hydroxypropyl cellulose (HPC)
Cellulose derivatives such as methylcellulose (MC) Water-soluble chitosan (can also be classified as “2. Natural polymers”)

Moreover, as a specific compound of the water-soluble polymer, for example, polyrotaxane can be mentioned. Polyrotaxane is cyclic at both ends (both ends of a linear molecule) of a pseudopolyrotaxane in which the opening of a cyclic molecule (rotator) is skewered by a linear molecule (axis). A blocking group is arranged so that the molecule is not released. For example, polyrotaxane using α-cyclodextrin as a cyclic molecule and polyethylene glycol as a linear molecule can be used.

Further, as the water-soluble polymer medium, a compound having a group that reacts with a crosslinking agent is more preferable because a strong film is formed by crosslinking.
In order to form a finely shaped pattern using the composition or the conductive material, the water-soluble polymer is preferably photocrosslinkable.

The molecular layer of the ionic liquid enclosing the carbon nanomaterial may be a monomolecular layer. Carbon nanomaterial surface and ionic liquid molecules are bonded by “cation-π” interaction, but the bonds between ionic liquid molecules are smaller than those by “cation-π” interaction. By selecting a combination of the material and the ionic liquid, the molecular layer of the ionic liquid enclosing the carbon nanomaterial can be made a monomolecular layer.
For example, by selecting carbon nanotubes as the carbon nanomaterial and N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF ₄ ) as the ionic liquid, DEMEBF ₄ enclosing the carbon nanotubes The molecular layer can be a monomolecular layer. Furthermore, when, for example, polyrotaxane is selected as the water-soluble polymer, a thin polyrotaxane layer of about 5 nm can be formed on the monomolecular layer of DEMEBF ₄ . The composition thus obtained can make the dispersion concentration of the carbon nanotubes high, and can be a highly conductive material. In a conductive member such as an electronic contact made of such a conductive material, electrons move between the carbon nanotubes through the thin DEMEBF ₄ molecular layer and the polyrotaxane layer, and a current flows.

In the conductive material, since the surface of the carbon nanomaterial and the molecule of the ionic liquid are strongly bonded by the “cation-π” interaction, the molecule of the ionic liquid bonded to the surface of the carbon nanomaterial is water-soluble. Does not come out of the conductive polymer medium. In addition, the molecule | numerator of the ionic liquid which is not couple | bonded with the surface of carbon nanomaterial can be removed by the rinse by the physiological saline or ethanol, for example.

According to the conductive material, the carbon nanomaterial contained therein is doubly covered with the ionic liquid molecule and the water-soluble polymer. There is virtually no touch. Further, since it has high flexibility, it has excellent followability with respect to the surface of an organ or the like in a living body, and an extremely good interface can be formed between the organ and the like. Furthermore, it can have a high electrical conductivity.

The conductive material is a first step in which a hydrophilic ionic liquid, a carbon nanomaterial, and water are mixed to obtain a first dispersion system in which the carbon nanomaterial covered with molecules constituting the ionic liquid is dispersed. And a first dispersion system, a water-soluble polymer and water are mixed to obtain a second dispersion system in which the carbon nanomaterial covered with the molecules constituting the ionic liquid and the water-soluble polymer are dispersed. It can manufacture by a manufacturing method provided with 2 processes.

In the first step, the carbon nanomaterial may be subdivided by applying a shearing force.
Thereby, the bundle or aggregation of the carbon nanomaterial can be covered with the hydrophilic ionic liquid in a state where the carbon nanomaterial is further unmelted.

After the second step, the method further comprises the step of crosslinking the water-soluble polymer, the carbon nanomaterial being dispersed in the water-soluble polymer medium, and producing a composition in which the water-soluble polymer is crosslinked. Also good. Thereby, a moldability and workability improve.
A rinsing step may be further provided to remove molecules constituting the ionic liquid that are not bonded to the carbon nanomaterial. Thereby, a moldability and workability improve.
This rinsing step can be performed with, for example, physiological saline, ethanol, or a liquid that does not break the gel. This rinsing process may be performed at any stage.

In addition, the said electroconductive material can contain another substance in the range which does not impair the effect of this invention. Moreover, the manufacturing method of the said electroconductive material can include another process in the range which does not impair the effect of this invention.

The conductive material will be specifically described based on examples. However, these examples are merely disclosed for the purpose of easily understanding the present invention, and the present invention is not limited thereto.

FIG. 5A shows carbon nanotubes covered with molecules constituting N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF ₄ ) dispersed in polyrotaxane. It is a photograph which shows the state of the composition before ultraviolet (UV) curing. It can be seen that the obtained composition is in the form of a gel (in the present specification, the term “gel” refers to a state in which the fluidity is lost or the fluidity is substantially reduced with respect to the fluid liquid. Meaning lost.)
This composition was prepared by using 30 mg of commercially available carbon nanotubes (MWNT, length 10 μm, diameter 5 nm) and N, N-diethyl-N-methyl-N- (2-methoxyethyl), which is a hydrophilic ionic liquid. The mixture was mixed with 60 mg of ammonium tetrafluoroborate (DEMEBF ₄ ), and stirred in deionized water at 25 ° C. for 1 week at a rotation speed of 700 rpm or more using a magnetic stirrer. The resulting suspension was treated with a high pressure jet mill homogenizer (60 MPa; Nano-jet pal, JN10, Jokoh) to give a black material. After rinsing the solution containing the obtained CNT gel with physiological saline, 1 mg of a photocrosslinking agent (Irgacure 2959, manufactured by Nagase Sangyo Co., Ltd.), polyrotaxane gel (“photocrosslinkable oscillating gel”, Advanced Soft Materials Co., Ltd.) The above composition was prepared by mixing 1000 mg.

FIG. 5B is a photograph of a sheet obtained by curing the composition shown in FIG. 5A by irradiating with ultraviolet rays (wavelength: 365 nm) for 5 minutes.
The Young's modulus of the obtained sheet was lower than 10 kPa. Since the Young's modulus of silicon is about 100 GPa and the Young's modulus of a conventional plastic film is 1 to 5 GPa, it can be seen that it is very soft. In addition, since the Young's modulus of the brain is 1 to 2 kPa and the Young's modulus of the cardiac muscle cells is ˜100 kPa, the composition or the conductive material of one embodiment of the present invention has the same level or higher than that of the organ. It was found to have a high softness. For this reason, it has high followability on the surface of the organ and can form an extremely good interface with the organ.

FIG. 5 (c) shows a case where photocrosslinking is performed using an ultrafine digital UV exposure system (“Digital Exposure Apparatus”, manufactured by PMT Corporation) and a fine structure having a line width of about 50 μm is patterned. It is an optical micrograph. The composition or the conductive material is thus a material that can be finely processed.
Since it can bridge | crosslink by various wavelengths by changing the kind of photocrosslinking material, it is not limited to UV.

FIG. 6 is a high-resolution cross-sectional transmission electron microscope image (TEM image), (a) is a TEM image of carbon nanotubes ((MWNT, length 10 μm, diameter 5 nm) that can be used in the present invention, (b) Without an ionic liquid, 30 mg of carbon nanotubes ((MWNT, length 10 μm, diameter 5 nm)) and 100 mg of polyrotaxane (“photocrosslinkable oscillating gel”, manufactured by Advanced Soft Materials Co., Ltd.) are mixed in water, and a jet mill A TEM image of carbon nanotubes covered with polyrotaxane, obtained by stirring while subdividing in FIG. 1, (c) is a composition obtained under the same conditions as the preparation conditions of the composition shown in FIG. It is a TEM image of.
As a high-resolution cross-sectional transmission electron microscope, HF-2000 Cold-FE TEM (80 kV, manufactured by Hitachi High-Technologies Corporation) was used.

As shown in FIG. 6A, it can be seen that the carbon nanotubes used consisted of three or four layers.
As shown in FIG. 6B, it is understood that the single carbon nanotube is coated with polyrotaxane, but the layer thickness of the coating layer is not uniform. In contrast, as shown in FIG. 6 (c), the layer thickness of the polyrotaxane layer covering the single carbon nanotube is very uniform, and it can be seen that it is clearly different from that shown in FIG. 6 (b).
The difference in the uniformity of the thickness of the coating layer is that the molecule of the hydrophilic ionic liquid DEMEBF ₄ that covered the carbon nanotubes was peeled off, and the polyrotaxane covered the carbon nanotubes instead of covering the carbon nanotubes. It shows that the polyrotaxane is covered on the molecular layer of the hydrophilic ionic liquid DEMEBF ₄ that has been used. If the molecules of the hydrophilic ionic liquid DEMEBF ₄ covering the carbon nanotubes are peeled off and the polyrotaxane covers the carbon nanotubes, the thickness of the coating layer in FIG. 6C is the same as in FIG. 6B. Should be uneven. Further, since the bond between the carbon nanotube and the molecule of DEMEBF ₄ is bonded by a high cation-π interaction comparable to a hydrogen bond, the molecule of the hydrophilic ionic liquid DEMEBF ₄ covering the carbon nanotube is the above-described process. Then it is thought that it is not peeled off.

As shown in FIG. 6, according to the method for producing the conductive material, the surface of the carbon nanotube can be uniformly coated with the biocompatible material via the molecules of the ionic liquid.

FIG. 7 is a graph showing the sheet resistance of the composition (CNT-gel) and the dependence of the sheet resistance on the carbon nanotube content. For comparison, the surface resistance of a gel based on conventional saline (Saline-based gel) is also indicated by a dotted line.
The composition (CNT-gel) is a composition obtained under the same conditions as those for producing the composition shown in FIG. The size was 1 cm square and the thickness was 1 mm.
A saline-based gel (Saline-based gel) was obtained by adding 1 mg of a photocrosslinking agent to 300 mg of rotaxane gel, dissolving in 100 ml of physiological saline, and then photocrosslinking with UV. . The size was 1 cm square and the thickness was 1 mm.
As shown in FIG. 7, the sheet resistance of the composition was found to be 2 to 3 orders of magnitude lower than that of the conventional gel.

FIG. 8 is a graph showing the electric capacity of the composition (CNT-rotaxane gel) and the frequency dependence of the electric capacity. For comparison, polyacrylamide gel (Poly-acrylamide gel), saline-containing polyacrylamide gel (Saline poly-acrylamide gel), and saline-containing rotaxane gel (Saline-rotaxane gel) were also shown.
The composition (CNT-rotaxane gel) is a composition obtained under the same conditions as those for producing the composition shown in FIG. The size was 1 cm square and the thickness was 1 mm.
A polyacrylamide gel was obtained by adding 1 mg of a photocrosslinking agent to 300 mg of polyacrylamide, dissolving in 100 ml of physiological saline, and then photocrosslinking with UV. The size was 1 cm square and the thickness was 1 mm.
Saline-containing polyacrylamide gel (Saline poly-acrylamide gel was obtained by adding 1 mg of a photocrosslinking agent to 300 mg of polyacrylamide, dissolving in 100 ml of physiological saline, and then photocrosslinking with UV. The thickness was 1 cm square and the thickness was 1 mm.
Saline-rotaxane gel was obtained by adding 1 mg of a photocrosslinking agent to 300 mg of rotaxane gel, dissolving in 100 ml of physiological saline, and then photocrosslinking with UV. The size was 1 cm square and the thickness was 1 mm.
As shown in FIG. 8, it was found that the electric capacity of the composition was higher than that of the gel of the comparative example.

When an electrical signal is detected by capacitive coupling, the magnitude is proportional to the surface area of the electronic contact. When an electronic contact is formed with the composition and an electrical signal is detected by capacitive coupling using the electronic contact, the composition is much softer than a conventional metal electronic contact, and the electronic contact is perfect for living tissue. The contact area can be increased due to the fact that they can stick to each other. Therefore, the detection sensitivity of a substantial capacity for obtaining an electric signal is very high as compared with a conventional metal electronic contact, and even a smaller electronic contact has a high detection capability.
In addition, the composition or the conductive material includes a carbon nanomaterial, and since the carbon nanomaterial, particularly the carbon nanotube has a high specific surface area, it has a high signal detection capability also in this respect. In addition, the conductivity of an electronic contact manufactured using the composition or the conductive material is lower than the conductivity of an Au electronic contact, but when the signal is taken by capacitance, it is not the conductivity but has a large effective surface area. This is very important.

In the following, carbon nanotubes are used as carbon nanomaterials, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate (DEMEBF ₄ ) is used as an ionic liquid, and polyrotaxane is used as a water-soluble polymer. A method for manufacturing the conductive material will be described with reference to FIG.
(1) First Step First, carbon nanotubes, DEMEBF ₄ and water are mixed and stirred to obtain a first dispersion system in which carbon nanotubes covered with molecules constituting the ionic liquid are dispersed.
The step of rinsing the first dispersion with physiological saline, ethanol, a liquid that does not break the gel, or the like may be performed to remove DEMEBF ₄ that is not bound to the carbon nanotubes.
In this dispersion system, the carbon nanotubes covered with the molecules constituting the ionic liquid are dispersed in water, and depending on the amount of the carbon nanotubes and the ionic liquid, other than the molecules constituting the ionic liquid are sufficient. In some cases, carbon nanotubes that are not covered or not covered at all (including bundled carbon nanotubes) and molecules that form an ionic liquid are contained.
In this step, it is preferable to apply a shearing force to the carbon nanotubes by a jet mill or the like to subdivide them. Through this process, the carbon nanotubes are bundled by van der Waals force, so that each carbon nanotube is unwound, the degree of bundling (aggregation) is reduced, and each carbon nanotube is unraveled to a single carbon nanotube. It is also possible.

FIG. 11 shows the results of examining the dispersibility of the carbon nanotubes. (A) shows a state after 30 mg of carbon nanotubes are put in deionized water at 25 ° C. and stirred for 1 week at a rotation speed of 700 rpm or more using a magnetic stirrer, and (B) shows 30 mg of carbon nanotubes and 60 mg of DEMEBF _4. And (C) is a state after stirring for 1 week in the same manner at 25 ° C., and (C) is the same as above. A state after being treated with a high-pressure jet mill homogenizer (60 MPa; Nano-jet pal, JN10, Jokoh), (D) shows 30 mg of carbon nanotubes and 60 mg of DEMEBF ₄ in 25 ° C. deionized water. (E) Carbon after stirring for 1 week and then treated with a high-pressure jet mill homogenizer And Bruno tube 30mg, and DEMEBF ₄ 60mg, microfibrillated cellulose (10% cellulose-containing aqueous solution 100mg, "Celish (trade name)" manufactured by Daicel Chemical Industries, Ltd.) and placed in deionized water 25 ° C., in the same manner 1 shows a state after the paste obtained by stirring for one week is processed with a high-pressure jet mill homogenizer, and is a photograph taken one week after the stirring is completed. “Serisch (trade name)” is cellulose nanofiber made from highly purified pure plant fiber as a raw material and microfibrillated by a special treatment method. The raw fiber is torn into tens of thousands by this treatment. The fiber thickness is refined to 0.1-0.01 μm.

(D) and (E) show that the carbon nanotubes show high dispersibility in water. It can be seen that it is preferable to subdivide the bundled carbon nanotubes by applying a shearing force in order to obtain high dispersibility.

(2) Second Step Next, the first dispersion, polyrotaxane (“photocrosslinkable tumbling gel”, manufactured by Advanced Soft Materials Co., Ltd.) and water are mixed and stirred, and the ionic liquid is mixed. A second dispersion system is obtained in which the carbon nanomaterial covered with the constituent molecules and the water-soluble polymer are dispersed.
The step of rinsing the second dispersion with saline, ethanol, a liquid that does not break the gel, or the like may be performed to remove DEMEBF ₄ that is not bound to the carbon nanotubes.
In addition, as shown in FIG. 9, when bridge | crosslinking the obtained composition, a crosslinking agent can also be mixed. Thus, the obtained second dispersion is a gel-like substance as shown in FIG.

(3) Crosslinking step Next, the polyrotaxane is crosslinked to obtain a composition (conductive material) in which the carbon nanotubes covered with the molecules constituting the DEMEBF ₄ are dispersed in the polyrotaxane medium, and the polyrotaxane is crosslinked. .
A step of rinsing the obtained composition (conductive material) with physiological saline, ethanol, a liquid that does not destroy the gel, or the like may be performed to remove DEMEBF ₄ that is not bonded to the carbon nanotubes.

Through the above steps, the composition (conductive material) can be obtained.

Next, an example of a process for forming a sheet made of the composition (conductive material) and a line having a fine line width made of the composition (conductive material) using the second dispersion system will be described. To do.

As shown in FIG. 10A, the second dispersion system is cast (cast) onto a glass substrate.
Next, as shown in FIG. 10B, a cover glass is placed on the glass substrate via a spacer sheet having a desired thickness (50 μm in the illustrated example).

Next, when producing a sheet, as shown in FIG. 10C, for example, a sheet having a thickness of 50 μm can be obtained by exposure using an ultraviolet (365 nm) exposure apparatus.
When forming a line with a fine line width, as shown in FIG. 10D, for example, by using a digital ultraviolet (365 nm) exposure apparatus, for example, a line with a width of 50 μm is formed. Can be formed.

(Multi-point probe array)
FIG. 12 is a perspective view showing an example of a multipoint probe array according to an embodiment of the present invention.
In the multipoint probe array 200, a plurality of the multipoint probes 100 described above are provided on the base substrate 30 so as to be spaced apart from each other. In FIG. 5, six multipoint probes 100 can be erected, but in the figure, only one is drawn for convenience.

The multipoint probe 100 is configured not to be wound around the other end 10b of the electronic contact sheet 10 so that an external circuit can be easily connected to the pad. The multipoint probe 100 is erected by inserting the other end 20 c of the core member 20 into a groove 32 provided in the base substrate 30.
The material of the base substrate 30 is preferably a workable ceramic such as zirconia or glass epoxy, but a single crystal silicon substrate or a glass substrate can also be used. The base substrate is provided with a plurality of grooves 32 for precisely positioning the multipoint probe 100. A mounting terminal (corresponding to the pad) formed on the base substrate 30 with the multipoint probe 100 fitted in the groove 32 so that the pad formed on the other end of the electronic contact sheet 10 faces the base substrate 30 side. It is electrically connected in a state of being aligned with (not shown). The mounting terminals are electrically connected to an electrical connector 31 fixed to the base substrate 30 through wiring formed on the base substrate 30.
Further, the pads of the electronic contact sheet 10 and the flexible cable may be directly connected without forming the wiring or the electrical connector 31 on the base substrate 30. In this case, the end portion of the electronic contact sheet 10 is bonded and fixed in a state where the pad is wound so that the pad faces the upper surface from the base substrate.

(Manufacturing method of multi-point probe)
Below, an example of the manufacturing method of the multipoint probe which concerns on one Embodiment of this invention is demonstrated.
First, a sheet-like insulating base material having a predetermined shape is prepared. Specifically, for example, a commercially available polyimide film or polyethylene naphthalate film is prepared.
Next, on one surface of the sheet-like insulating substrate, using a known circuit creation technique, a plurality of electronic contacts, a plurality of wirings connected to each electronic contact, and a plurality of wirings connected to each wiring And a pad. As a known circuit creation technique, for example, a flexible printed circuit board creation technique can be cited.
Next, a layer made of a first insulating material is formed on the substrate on which the circuit is formed so as to expose the electronic contacts and the pads.
Next, one end of the electronic contact sheet is fixed to the outer peripheral surface of the core material using, for example, a cyanoacrylate adhesive, and winding is started. Use to bond the front and back surfaces of the electronic contact sheet, continue winding, and finally use the back of the other end of the electronic contact sheet, for example, using the same epoxy adhesive Adhere to the surface and complete the winding.
Next, a second insulating material such as parylene is entirely covered, and the second insulating material on the electronic contact and the pad is removed using a laser or the like to expose the electronic contact and the pad.
A multipoint probe can be manufactured by the above-described steps.

(Manufacturing method of multi-point probe array)
An example of a method for manufacturing a multipoint probe array according to an embodiment of the present invention will be described using the flowchart of the manufacturing process shown in FIG. A part of the manufacturing method may be applied to a method for manufacturing a multi-point probe, and a part of the manufacturing method for the multi-point probe described above may be applied to the following method for manufacturing a multi-point probe array. You may apply to.
First, a sheet-like insulating substrate such as a polyimide film is pasted on a support substrate such as a flat glass substrate (step (a)).
Next, a planarization layer using, for example, parylene or the like is formed by CVD on one surface of the sheet-like insulating base (step (b)).
Next, a plurality of electronic contacts, a plurality of wirings connected to each electronic contact, and a plurality of pads connected to each wiring are formed on the planarizing layer by mask vapor deposition to form an electronic contact sheet. (Step (c)).
Next, the entire electronic contact sheet on which the circuit is formed is covered with a first insulating material (step (d)), and then the first insulating material on the electronic contacts and the pads is removed (step (e)). .
Next, the sheet-like insulating base material (electronic contact sheet) is inverted and transferred to another support substrate (step (f)), for example, on one end of the surface that has been attached to the previous support substrate. Then, an adhesive such as a cyanoacrylate adhesive is applied (step (g)).
Next, the core material is fixed to the portion of the electronic contact sheet to which the adhesive is applied (step (h)), the electronic contact sheet is wound around the core material, and finally the back surface of the other end of the electronic contact sheet is An epoxy adhesive is used to adhere to the front surface of the electronic contact sheet to complete winding (step (i)).
Next, a second insulating material such as parylene is entirely covered, the second insulating material on the electronic contact and the pad is removed with a laser, etc., and the electronic contact and the pad are exposed to manufacture a multipoint probe. To do.
Next, the multipoint probe is fixed to the groove of the base substrate (step (j)).
Next, the pads of the multipoint probe are mounted on the terminals of the base substrate (step (k)).
A multipoint probe array can be manufactured by the above-described steps.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to this embodiment. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit of the present invention. The present invention is not limited by the foregoing description, but only by the appended claims.

1 sheet-like insulating substrate 1a one side 1c edge 2 electronic contact 3, 3a, 3b, 3c wiring 4 pad 10 electronic contact sheet 10a one end 10b other end 20 core material 20a outer peripheral surface 20b one end 20c other end 30 base substrate 100 Multipoint probe 200 Multipoint probe array

Claims (14)

1. An electronic contact sheet having a plurality of electronic contacts arranged in a row and spaced apart on a sheet-like insulating base and a plurality of wires connected to each electronic contact, from one end to the other end A multi-point probe composed of a tubular laminate formed by laminating multiple layers by winding,
   The electronic contacts are exposed without being covered with the sheet-like insulating base material, and the wiring is laminated so that at least a part thereof is covered with the sheet-like insulating base material except for the uppermost layer wiring. A multipoint probe characterized by that.
2. The multipoint probe according to claim 1, further comprising an axial core material, wherein the electronic contact sheet is wound around an outer peripheral surface of the core material.
3. The said some electronic contact is arrange | positioned along the edge part of the one end side of the said electronic contact sheet in one surface of the said sheet-like insulation base material, Either of Claim 1 or 2 characterized by the above-mentioned. The multipoint probe described in 1.
4. 4. The sheet-like insulating base material according to claim 1, wherein the edge portion is formed so as to recede from one end to the other end of the tubular laminated body. 5. The multipoint probe described.
5. The multipoint probe according to any one of claims 1 to 4, wherein the plurality of electronic contacts are arranged in a spiral shape with respect to an axis of the tubular laminate.
6. 6. The plurality of wires are extended along the axial direction of the tubular laminated body over a predetermined range starting from the plurality of electronic contacts. 6. Multipoint probe.
7. A plurality of pads connected to each wiring and connected to an external circuit are arranged along the other end in the vicinity of the other end of the electronic contact sheet. The multipoint probe according to one item.
8. 8. The electronic contact sheet is coated with a first insulating material so that the plurality of electronic contacts and the plurality of pads are exposed. 9. Multipoint probe.
9. The multi-point probe according to claim 8, wherein a first shield conductive film is formed on the other surface of the sheet-like insulating substrate on which the wiring is disposed.
10. The multipoint according to any one of claims 1 to 9, wherein a second shield conductive film is formed on a surface of the sheet-like insulating base material on which the wiring is disposed. probe.
11. The multipoint probe according to any one of claims 1 to 10, wherein the sheet-like insulating base material includes an amplifier connected to the plurality of electronic contacts.
12. A multi-point probe array, wherein a plurality of the multi-point probes according to any one of claims 1 to 11 are provided on the base substrate so as to be spaced apart from each other.
13. An electronic contact sheet constituting the multipoint probe according to any one of claims 1 to 11.
14. It is a manufacturing method of the multipoint probe as described in any one of Claim 1 to 11,
    The electronic contact sheet is wound from one end to the other end so that the plurality of electronic contacts are exposed, and then entirely covered with a second insulating material, and then the plurality of electronic contacts and the plurality of electronic contacts are covered. A method of manufacturing a multipoint probe, wherein the second insulating material on the pad is removed.

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